EP0467760A1

EP0467760A1 - Pyrimidine derivatives, methods for producing them, and fungicides, insecticides and/or acaricides containing them as active ingredient

Info

Publication number: EP0467760A1
Application number: EP91401939A
Authority: EP
Inventors: Tsuguhiro Katoh; Hirotaka Takano; Hiroaki Fujimoto; Hirosi Kisida
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 1990-07-18
Filing date: 1991-07-11
Publication date: 1992-01-22
Also published as: NZ238817A; KR940005022B1; AU638144B2; AU8045991A; KR920002557A

Abstract

A compound which is effective as an active ingredient of fungicides, insecticides and/or acaricides, and is represented by the formula and a method for preparing the same are provided:

wherein R₁ represents a lower alkyl group, R₂ represents a lower alkyl group or a halogen atom, or R₁ and R₂ are bonded together at their termini and represent trimethylene or tetramethylene, R₃ represents a hydrogen atom, a lower alkyl group or a halogen atom, R₄ represents a hydrogen atom or a lower alkyl group, R₅ represents a hydrogen atom, a lower alkyl group or a methylthio group and n represents 2 or 3.

Description

The present invention relates to pyrimidine derivatives, a method for producing them, and fungicides, insecticides and/or acaricides which contain them as an active ingredient.
Japanese Patent Kokai Nos. 63-156781 and 55-76804, etc. disclose that some of pyrimidine derivatives have fungicidal, insecticidal and/or acaricidal activities. However, activities of these compounds as fungicides, insecticides, and/or acaricides are not necessarily satisfactory.
Under the circumstances, the inventors have conducted intensive research and have found that the pyrimidine derivatives represented by the following formula (I) have excellent fungicidal, insecticidal and/or acaricidal activities. As a result, the present invention has been accomplished.
That is, the present invention provides pyrimidine derivatives (hereinafter referred to as "the present compounds") represented by the formula:

wherein R₁ represents a lower alkyl group, R₂ represents a lower alkyl group or a halogen atom, or R₁ and R₂ are bonded together at their termini and represent a trimethylene group or a tetramethylene group, R₃ represents a hydrogen atom, a lower alkyl group or a halogen atom, R₄ represents a hydrogen atom or a lower alkyl group, R₅ represents a hydrogen atom, a lower alkyl group or a methylthio group, and n represents 2 or 3, a method for producing them, and fungicides, insecticides and/or acaricides containing them as an active ingredient.
In the above formula (I), the lower alkyl group includes alkyl groups of 1-4 carbon atoms such as, for example, methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl group.
The halogen atom includes fluorine atom, chlorine atom, bromine atom and iodine atom.
With reference to the substituents in the formula (I), the following can be mentioned from the points of fungicidal, insecticidal and/or acaricidal activities, etc.
Among the present compounds, preferred are those which are represented by the formula (I) where R₁ represents an ethyl group and R₂ represents an ethyl group, a chlorine atom, or a bromine atom, or R₁ and R₂ are bonded together at their terminals to form a trimethylene group or a tetramethylene group and where R₃, R₄ and R₅ each represents a hydrogen atom, or R₃ and R₄ each represents a hydrogen atom and R₅ represents a methyl group or a methylthio group, or R₃ represents a methyl group and R₄ and R₅ each represents a hydrogen atom, or R₃ and R₄ each represents a methyl group and R₅ represents a hydrogen atom or a methyl group. So far as R₁ and R₂ are concerned, compound wherein R₁ is an ethyl group and R₂ is a chlorine atom are preferred, those wherein R₁ and R₂ each is an ethyl group are more preferred and those wherein R₁ and R₂ bond together at their terminals to form a tetramethylene group or a trimethylene group are the most, in view of their fungicidal activities and undesirable influence upon plants. This order is, however, reversed from a standpoint of acaricidal activity. So far as R₃, R₄ and R₅ are concerned, preferred one is a compound wherein R₃ is a methyl group and R₄ and R₅ each is a hydrogen atom. A compound wherein R₃ and R₄ each is a methyl group and R₅ is a hydrogen atom or a methyl group is preferred as acaricides. The suffix "n" is preferably 2.
The present compounds exhibit controlling effects in preventive, curative and systemic controlling effects against various plant diseases. The following are plant diseases against which the present compound has a controlling effect.
Pyricularia oryzae, Cochliobolus miyabeanus and Rhizoctonia solani of rice; Erysiphe graminis, f. SP. hordei, f. SP. tritici, Gibberella zeae, Puccinia striiformis, P. graminis, P. recodita, P. hordei, Typhula sp., Micronectriella nivalis, Ustilago tritici, U. nuda, Tilletia caries, Pseudocercosporella herpotrichoides, Rhynchosporium secalis, Septoria tritici and Leptosphaeria nodorum of wheat; Diaporthe citri, Elsinoe fawcetti, Penicillium digitatum and P. italicum of citrus fruits; Sclerotinica mail, Valsa mail, Podpsphaera leucotricha, Alternaria mail and Venturia inaequalis of apple; Venturia nashicola, V. pirina, Alternaria kikuchiana and Gymnosporangium haraeanum of Pear; Sclerotinia cinerea, Cladosporium carpophilum and Phomopsis sp. of peach; Elsinoe ampelina, Glomerella cingulata, Uncinula necator, Phakopsora ampelopsidis, Guignardia bidwellii and Plasmopara viticola of grape; Gloeosprorium kaki, Cercospora kaki and Mycosphaerella nawae of persimmon; Colletotrichum lagenarium, Sphaerotheca fuliginea, Mycosphaerella melonis, Pseudoperonospora cubensis and Phytophthora sp. of cucumber; Alternaria solani, Cladosporium fulvum and Phytophthora infestans of tomato; Phomopsis vexans and Erysiphe cichoracearum of eggplant; Alternaia japonica and Cercosporella brassicae of rape vegetable; Puccinia allii of Welsh onion; Cercospora kikuchii, Elsinoe glycines and Diaporthe phaseolorum var. sojae of soybean; Colletotrichum lindemthianum of kidney bean;Mycosphaerella personatum and Cercospora arachidicola of peanut; Erysiphe pisi of pean; Alternaria solani and Phytophthora infestans of potato; Sphaerotheca humuli of strawberry; Exobasidium reticulatum and Elsinoe leucospila of tea plant; Alternaria longipes, Erysiphe cichoracearum, Colletotrichum tabacum, Peronospora tabacina and Phytophthora nicotianae of tabacco; Cercospora beticola of beet; Diplocarpon rosae and Sphaerotheca pannosa of rose; Septoria chrysanthemi-indici and Puccinia horiana of chrysanthemum; and Botrytis cinerea and Sclerotinia sclerotiorum of various crops.
Among them, the present compounds are especially effective against downy mildew and late blight of various plants.
The following are harmful insects and acarines against which the present compounds are effective.
Hemiptera:
Planthoppers such as small brown planthopper, brown rice planthopper and white backed rice planthopper; leafhoppers such as green rice leaf-hopper and Formosan green rice leafhopper; aphids; stinkbugs; whiteflies; scales; lace bugs; and jumping plantlices.
Lepidoptera (moths and butterflies):
Pyralid moths such as rice stem borer, rice leafroller and Plodia interpunctella; cutworms such as tobacco cutworm, armyworm and cabbage armyworm; whites and sulfer butterflies such as common white;Tortricidae such as Archips xyiosteanus; Carposinidae; lyonetiid moths; tussock moths; Agrothis spp. such as cutworm and black cutworm; Heliothis spp.; diamondback moth; casemaking clothes moth; and webbing clothes moth.
Diptera (flies):
House mosquitos such as northern house mosquito and Culex tritaeniorhynchus; Aedes spp. such as Aedes aegypti and Aedes albo-pictus; Anopheles spp.. such as Anopheles sinensis; Chironomidae; Muscidae such as housefly and Muscina stabulanu; Calliphoridae (blow-flies); Sarcophagidae; anthomyid flies such as fannia, seedcorn maggot and onion maggot, fruit flies; vinegar flies; moth flies; gadflies; gnats; and stable flies.
Coleoptera (beetles):
Corn root worms such as western corn root worm and southern corn root worm; scarabs such as cupreous chafer and soybean beetle; snout beetles or weevils such as maize weevil and rice water weevil; darkling beetles such as yellow mealworm and red flour beetle; leaf beetles such as striped flea beetle and curcurbit leaf beetle; deathwatch and drugstore beetles; Henosuepilacha spp. such as twenty-eight-spotted lady bird; powderpost beetles; false powderpost beetles; and longicorn beetles.
Dictyoptera:
German cockroach, smokybrown cockroach, American cockroach, Periplaneta brunnea and Blatta orientalis.
Thysanoptera (thrips):
Thrips palmi and flower thrips.
Hymenoptera:
Ants; hornets; bethylid wasps; and sawflies such as cabbage sawfly.
Orthoptera:
Mole crickets and grasshoppers.
Aphaniptera:
Pulex irritans.
Anopiura:
Pediculus humanus and Phthirus pubis.
Isoptera:
Reticulitermes speratus and Formosan subterranean termite.
Spider mites:
Carmine spider mite, twospotted spider mite, Kanzawa spider mite, citrus red mite and European red mite.
Ticks:
Boophilus microplus.
House dust mites:
Acarid mites,Pyroglyphidae, Cheyletidae and Ornithanyssus bacoti.
The present compounds are effective especially on spider mites.
process for production of the present compounds will be explained in detail.
The present compounds can be produced by reacting a halopyrimidine derivative represented by the following formula (II):

wherein R₁, R₂ and Y have the same meanings as above, with an amine derivative represented by the following formula (III):

wherein R₃, R₄, R₅ and n have the same meanings as above, if necessary, in the presence of a base.
Reaction temperature is usually from room temperature to about 250°C, preferably 50°C to 200°C and reaction time is about 10 minutes to about 12 hours.
With reference to the amount of the materials used for the reaction, amount of the amine derivative represented by the formula (III) is 1-5 mols, more preferably 1-2 mols based on 1 mol of the halopyrimidine derivative represented by the formula (II) and, if necessary, 1-2 mols of a base can be used. Examples of the base are alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates such as sodium carbonate, organic bases such as triethylamine, N,N-diethylaniline, pyridine, and diazabicycloundecene, and mixtures thereof. When the amine derivative represented by the formula (III) is used in an excess amount in the reaction, this excess amine derivative per se can be used as the base.
In the above reaction, reaction solvent is not necessarily required, but the reaction is generally carried out in the presence of a solvent. The solvent includes, for example, aromatic hydrocarbons such as benzene and toluene, halogenated aromatic hydrocarbons such as chlorobenzene, aliphatic hydrocarbons such as hexane and cyclohexane, halogenated aliphatic hydrocarbons such as chloroform, dichloromethane and dichloroethane, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, esters such as ethyl acetate, ethers such as diethyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether, alcohols such as methanol and ethanol, water, N,N-dimethylformamide, pyridine, and mixtures thereof.
After completion of the reaction, the reaction mixture is subjected to usual work-up such as concentration under reduced pressure and extraction and, if necessary, to purification operations such as chromatography and recrystallization, thereby to obtain the desired compound.
Examples of the present compounds which can be produced by the above-mentioned process are shown in Table 1.
The halopyrimidine derivative represented by the formula (II) which is one starting compound in preparation of the present compounds can be easily prepared by known methods such as the method described in Japanese Patent Kokai Nos. 63-156781 and 58-222070. The amine derivative represented by the formula (III) which is another starting compound in preparation of the present compounds can be prepared, for example, through the following reaction formulas.

(wherein R₃, R₄, R₅ and n have the same meanings as above and X represents a halogen atom.)
In the above reaction formulas, the phenol derivative represented by the formula (IV) which is an intermediate for preparation of the amine derivative represented by the formula (III) and wherein R₃ in the formula (IV) is a chlorine atom can also be prepared by the following reaction formula.

wherein R₄ and R₅ have the same meanings as above.
When the present compound is used as an active ingredient of fungicides, it may be used without adding any other components, but usually, it is formulated into emulsifiable concentrates, wettable powders, suspension formulations, dusts, granules and the like by mixing with a solid or liquid carrier, a surface active agent and other auxiliaries for formulation. In this case, the content of the present compound as an active ingredient in the formulations is 0.1 - 99.9 %, preferably 1 - 90 % by weight.
The solid carriers include, for example, fine powders or granules of kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn starch powder, walnut shell powder, urea, ammonium sulfate and synthetic hydrated silicon dioxide. The liquid carriers include, for example, aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol and cellosolve, ketones such as acetone, cyclohexenone and isophorone, vegetable oils such as soybean oil and cotton seed oil, dimethyl sulfoxide, acetonitrile, and water.
The surface active agents used for emulsification, dispersion, wetting, etc. include, for example, anionic surface active agents such as alkylsulfuric esters, alkylsulfonates, alkylarylsulfonates, dialkylsulfosuccinates, polyoxyethylene-alkylaryl ether phosphoric esters, and naphthalene-sulfonic acid/formalin condensates and nonionic surface active agents such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. The auxiliaries for formulation include, for example, lignosulfonates, alginates, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), and PAP (acid isopropyl phosphate).
When the present compound is used as an active ingredient of fungicides, its dosage is usually 0.1 - 100 g, preferably 0.2 - 20 g per 1 are. When the present compound is used in the form of emulsifiable concentrate, wettable powder, suspension formulation or the like which is diluted with water, the concentration is 0.0001 - 0.5 %, preferably 0.0005 - 0.2 %. Granules and dusts are used as they are without dilution.
The present compound can also be used as a seed disinfectant and besides, can be mixed with other fungicides to enhance fungicidal effect. Furthermore, the present compound can be used in admixture with insecticides, acaricides, nematocides, herbicides, plant growth regulating agents or fertilizers.
When the present compound is used as an active ingredient of insecticides and/or acaricides, it is mixed with a solid carrier, a liquid carrier, a gaseous carrier or a bait or is impregnated in base materials for mosquito coils and mats, if necessary, with addition of surface active agents and other auxiliaries for formulation, thereby to formulate into oil sprays, emulsifiable concentrates, wettable powders, flowable concentrates such as water-based suspension formulations and water-based emulsion formulations, granules, dusts, aerosols, heat fumigants such as mosquito coils, electric mosquito mats and electric non-mat formulation, heating smoking agents such as self-burning type smoking agents, chemical reaction type smoking agents and porous ceramic plate-type smoking agents, aerosols such as fogging, ULV agents, poison baits and the like.
These formulations usually contain the present compound in an amount of 0.001 - 95 % by weight as an active ingredient.
The solid carriers used in formulation include fine powders or granules of, for example, clays (such as kaolin clay, diatomaceous earth, synthetic hydrated silicon dioxide, bentonite, fubasami clay, and acid clay), talcs, ceramics, other inorganic minerals (such as sericite, quartz, sulfur, active carbon, calcium carbonate and hydrated silica) and chemical fertilizers (such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and ammonium chloride). The liquid carriers include, for example, water, alcohols (such as methanol and ethanol), ketones (such as acetone and methyl ethyl ketone), aromatic hydrocarbons (such as benzene, toluene, xylene, ethylbenzene and methylnaphthalene), aliphatic hydrocarbons (such as hexane, cyclohexane, kerosine and light oil), esters (such as ethyl acetate and butyl acetate), nitriles (such as acetonitrile and isobutyronitrile), ethers (such as diisopropyl ether and dioxane), acid amides (such as N,N-dimethylformamide and N,N-dimethylacetamide), halogenated hydrocarbons (such as dichloromethane, trichloroethane and carbon tetrachloride), dimethyl sulfoxide, and vegetable oils (such as soybean oil and cotton seed oil). The gaseous carriers, namely, propellants include, for example, Freon gas®, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide and the like.
The surface active agents include, for example, alkylsulfuricesters, alkylsulfonates, alkylarylsulfonates, alkylaryl ethers and polyoxyethylated products thereof, polyethylene glycol ethers, polyhydric alcohol esters and sugar alcohol derivatives.
The auxiliaries for formulation such as adhesive agents and dispersants include, for example, casein, gelatin, polysaccharides (such as starch powder, gum arabic, cellulose derivatives and alginic acid), lignin derivatives, bentonite, sugars and synthetic water-soluble polymers (such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylic acids). The stabilizers include, for example, PAP (acid isopropyl phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surface active agents and fatty acids or esters thereof.
As base materials for the poison bait, mention may be made of bait components such as grain flour, vegetable oil, sugar and crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, erroneous eating inhibitors such as capsicum powder and attractant perfumes such as cheese perfume and onion perfume.
Formulations of flowable concentrates (water-based suspension formulations or water-based emulsion formulations) are generally prepared by finely dispersing 1 - 75 % of the compound in water containing 0.5 - 15 % of a dispersing agent, 0.1 - 10 % of a suspension aid (such as protective colloid or compound which imparts thixotropic properties) and 0 - 10 % of a suitable auxiliary (such as antifoamer, rust preventive, stabilizer, spreader, penetrating aid, antifreezing agent, antimicrobial agent or mildewproofing agent). It is also possible to prepare oil suspension by using an oil in which the compound is hardly soluble in place of water. As the protective colloid, there may be used, for example, geranine, casein, gums, cellulose ether and polyvinyl alcohol. As the compounds which impart thixotropic properties, there may be used, for example, bentonite, aluminum magnesium silicate, xanthane gum and polyacrylic acid.
The resulting formulations are used as such or diluted with, for example, water. Furthermore, they can be used in admixture with other insecticides, acaricides, fungicides, herbicides, plant growth regulating agents, synergists, fertilizers, soil improvers and the like or they can be used together with these agents without being mixed therewith.
When the present compound is used as an active ingredient of agricultural insecticides and/or acaricides, its dosage is usually 0.1 - 500 g per 10 areas. When the emulsifiable concentrate, wettable powder, flowable concentrates, etc. are diluted with water for use, the concentration is 0.0001 - 1000 ppm. Granule and dust are used as they are without any dilution. When the present compound is used as an active ingredient of insecticides and acaricides for disinfestation, the emulsifiable concentrate, wettable powder and flowable concentrate are diluted to 0.0001 - 10000 ppm with water for use and the oil solution, aerosol, fumigant, smoking agent, fogging agent, ULV agent and poison bait are used as they are.
The dosage and concentration thereof depends on kind of formulation, time, method and place of application, kind of pests and state of diseases and can be increased or decreased regardless of the above-mentioned ranges.
The present invention will be explained in more detail by the following preparation examples, formulation examples and test examples. It should be understood that they should not be construed as limiting the invention.

Preparation Example 1

A mixture of 1.0 g of 4-chloro-5,6-tetra-methylenepyrimidine and 2.67 g of 2-(4-benzyl-phenoxy)ethylamine was stirred with heating at 150°C for 1 hour. After the mixture was left for cooling, 50 ml of water was added to the reaction mixture, followed by extracting with 50 ml of chloroform three times. The extract was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain an oily residue. This was chromatographed on a silica gel column (eluting solvent hexane : acetone = 3 : 1 (v/v)) to obtain 0.8 g of 4-[2-(4-benzylphenoxy)ethylamino]-5,6-tetramethylenepyrimidine (the present compound (4)).

Preparation Example 2

0.53 g of 4,5-dichloro-6-ethylpyrimidine and 0.87 g of 2-(4-benzyl-2-methylphenoxy)ethylamine were dissolved in 3 ml of toluene and 0.36 g of triethylamine was added thereto, followed by refluxing under heating for 2 hours. After leaving for cooling, 30 ml of water was added to the reaction mixture, followed by extracting with 30 ml of chloroform three times. The extract was dried over anhydrous magnesium sulfate and then, concentrated under reduced pressure to obtain an oily residue. This residue was chromatographed on a silica gel column (eluting solvent hexane : acetone = 3 : 1 (v/v)) to obtain 0.47 g of 4-[2-(4-benzyl-2-methylphenoxy)ethylamino]-5-chloro-6-ethylpyrimidine (the present compound (15)).

Preparation Example 3

A mixture of 1.0 g of 4-chloro-5,6-tetramethylenepyrimidine and 2.86 g of 2-(4-benzyl-2-methylphenoxy)ethylamine was subjected to reaction and treatment in the same manner as in Preparation Example 1 to obtain 0.75 g of 4-[2-(4-benzyl-2-methylphenoxy)ethylamino]-5,6-tetramethylenepyrimidine (the present compound (14)).

Preparation Example 4

A mixture of 1.0 g of 4-chloro-5,6-tetra-methylenepyrimidine and 3.1 g of 2-(4-benzyl-2-chlorophenoxy)ethylamine was subjected to reaction and treatment in the same manner as in Preparation Example 1 to obtain 1.1 g of 4-[2-(4-benzyl-2-chlorophenoxy)ethylamino]-5,6-tetramethylenepyrimidine (the present compound (7)).

Preparation Example 5

0.53 g of 4,5-dichloro-6-ethylpyrimidine and 0.92 g of 2-(4-benzyl-2,3-dimethylphenoxy) ethylamine were dissolved in 3 ml of toluene and subjected to reaction and treatment in the same manner as in Preparation Example 2 to obtain 0.51 g of 4-[2-(4-benzyl-2,3-dimethylphenoxy)ethylemino]-5-chloro-6-ethylpyrimidine (the present compound (17)).
The present compounds which were prepared in accordance with the above preparation examples are shown in Table 2.
Preparation examples of the starting compounds used for preparation of the present compounds are shown below.

Reference Example 1

Preparation of 2-(4-benzylphenoxy)ethylamine

(a) 18.4 g of 4-benzylphenol was dissolved in 100 ml of anhydrous tetrahydrofuran and 4.0 g of sodium hydride (60 % oil dispersion) was gradually added to the solution with ice cooling in nitrogen stream. The solution was stirred for 1 hour at room temperature and 12.0 g of bromoacetonitrile was added thereto under ice cooling, followed by refluxing with heating for 3 hours. After being left for cooling, the reaction mixture was concentrated under reduced pressure and to the residue was added 100 ml of water, followed by extracting twice with 100 ml of chloroform. The extract was washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain an oily residue. The residue was chromatographed on a silica gel column (eluting solvent hexane : acetone = 3 : 1 (v/v)) to obtain 19.1 g of (4-benzylphenoxy)acetonitrile.
(b) 3.4 g of lithium aluminum hydride was suspended in 100 ml of anhydrous tetrahydrofuran and to the suspension was gradually added 10.0 g of (4-benzylphenoxy)acetonitrile under ice cooling in nitrogen stream. After stirring at room temperature for 1 hour and ice cooling, to the reaction mixture were carefully added 3.4 ml of water, then 3.4 ml of 5N aqueous sodium hydroxide solution and finally 10 ml of water, followed by stirring for a while. Undesired matters were removed by filtration with cerite and the filtrate was concentrated under reduced pressure to obtain 9.8 g of 2-(4-benzyl-phenoxy)ethylamine. This was used for the subsequent reaction without further purification.

Reference Example 2
Preparation of 2-(4-benzyl-2-methylphenoxy)ethylamine

(a) Grignard reagent was prepared from 12.15 g of magnesium (turnings) and 50.23 g of 1-bromo-4-methoxy-3-methylbenzene in 200 ml of anhydrous ether by conventional process. To this Grignard reagent was added 200 ml of anhydrous benzene and ether was distilled off under normal pressure. To this solution was added dropwise a mixed solution comprising 47.25 g of benzyl chloride and 50 ml of anhydrous benzene under refluxing with heating, followed by stirring for 3 hours. After being left for cooling, the reaction mixture was filtered and the filtrate was washed with dilute hydrochloric acid, dilute aqueous sodium hydroxide solution and water in this order. The filtrate was dried over anhydrous magnesium sulfate and then was concentrated under reduced pressure and thereafter, distilled under reduced pressure to obtain 30.8 g of 4-benzyl-2-methyl-1-methoxybenzene.
(b) A mixture of 30.8 g of 4-benzyl-2-methyl-1-methoxybenzene with 50 ml of hydrobromic acid and 100 ml of acetic acid was refluxed with heating for 5 hours. This was left for cooling and neutralized with an aqueous sodium hydrogencarbonate solution and was extracted twice with 100 ml of ethyl acetate. The extract was dried over anhydrous magnesium sulfate and then was concentrated under reduced pressure. The resulting oily residue was chromatographed on a silica gel column (eluting solvent hexane:acetone = 3 : 1 (v/v)) to obtain 23.7 g of 4-benzyl-2-methylphenol.
(c) 2-(4-benzyl-2-methylphenoxy)ethylamine was prepared from 4-benzyl-2-methylphenol in the same manner as in Reference Example 1.

Reference Example 3

Preparation of 2-(4-benzyl-2-chlorophenoxy)ethylamine

(a) 18.4 g of 4-benzylphenol was dissolved in 100 ml of carbon tetrachloride and thereto was added dropwise 10.85 g of t-butyl hypochlorite at -5 -0°C with stirring. After stirring for 3 hours at room temperature, the reaction mixture was washed with a saturated aqueous sodium hydrogencarbonate solution and then with water, then dried over anhydrous magnesium sulfate and thereafter, concentrated under reduced pressure. The resulting oily residue was chromatographed on a silica gel column (eluting solvent hexane:acetone = 3 : 1 (v/v)) to obtain 20.6 g of 4-benzyl-2-chlorophenol.
(b) 2-(4-benzyl-2-chlorophenoxy)ethyl-amine was prepared from 4-benzyl-2-chlorophenol in the same manner as in Reference Example 1.

Next, formulation examples will be shown below, where part is by weight.

Formulation Example 1

50 parts of each of the present compounds (1) - (21), 3 parts of calcium lignosulfonate, 2 parts of sodium laurylsulfate and 45 parts of synthetic hydrated silicon dioxide are thoroughly pulverized and mixed to obtain a wettable powder.

Formulation Example 2

25 parts of each of the present compounds (1) - (21), 3 parts of polyoxyethylenesorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed and wet-pulverized until the particle size of the active ingredient reaches not more than 5 microns to obtain a suspension formulation.

Formulation Example 3

2 parts of each of the present compounds (1) - (21), 88 parts of kaolin clay and 10 parts of talc are thoroughly pulverized and mixed to obtain a dust.

Formulation Example 4

20 parts of each of the present compounds (1) - (21), 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 60 parts of xylene are thoroughly mixed to obtain an emulsifiable concentrate.

Formulation Example 5

2 parts of each of the present compounds (1) - (21), 1 part of synthetic hydrated silicon dioxide, 2 parts of calcium lignosulfonate, 30 parts of bentonite and 65 parts of kaolin clay are thoroughly pulverized and mixed, well kneaded with water, then granulated and dried to obtain a granule.

Formulation Example 6

10 parts of each of the present compounds (1) - (21) is dissolved in 35 parts of xylene and 35 parts of dimethylformamide and to the solution are added 14 parts of polyoxyethvlene styrylphenyl ether and 6 parts of calcium dodecylbenzenesulfonate, followed by well stirring and mixing to obtain an emulsifiable concentrate of 10 % in concentration.

Formulation Example 7

0.1 part of each of the present compounds (1) - (21) is dissolved in 5 parts of xylene and 5 parts of trichloroethane and the solution is mixed with 89.9 parts of deodorized kerosine to obtain an oil spray of 0.1 % in concentration.

Formulation Example 8

0.1 part of each of the present compounds (1) - (21), 0.2 part of tetramethrin, 0.1 part of d-phenothrin, 10 parts of trichloroethane and 59.6 parts of deodorized kerosene are mixed and dissolved. The solution is filled in an aerosol container, to which a valve portion is fitted. Then, 30 parts of a propellant (liquefied petroleum gas) is filled under pressure in the container through the valve portion to obtain an oil-based aerosol.
The following test examples demonstrate the effectiveness of the present compound as fungicides, insecticides and/or acaricides. The present compounds used in the test examples are identified by the compound numbers shown in Table 2 and the compounds used for comparison are identified by the compound symbols shown in Table 3.
First, the effectiveness of the present compounds as fungicides is shown by the following test examples.
The controlling effect was evaluated by visually observing the state of disease of the test plants, namely, degree of fungus colony and infected area on the leaves and stems of the test plants. The results of evaluation were expressed in terms of six ratings as follows:
"5" Not observed at all.
"4" Observed on about 10 % of the leaves and stems.
"3" Observed on about 30 % of the leaves and stems.
"2" Observed on about 50 % of the leaves and stems.
"1" Observed on about 70 % of the leaves and stems.
"0" Same as when no compound was used.

Test Example 1

Test for controlling effect on Phytophthora infestans of tomato (preventive controlling effect)
Tomato (Ponte rosa) seeds were sown in the sandy loam filled in a plastic pot. After raising for 20 days in a greenhouse, the seedlings with two foliage leaves were subjected to foliage application with a spray liquid of the wettable powder prepared according to Formulation Example 1 which was diluted with water to a given concentration so that the liquid was sufficiently applied to the surface of the leaves. After application, the seedlings were inoculated with zoospores of Phytophthora infestans of tomato by spraying a suspension containing the zoospores. The inoculated seedlings were kept at 23°C in a damp place overnight and were further grown for 4 days in a greenhouse. The controlling effect was examined. The results are shown in Table 4.

Test Example 2

Test for controlling effect on Plasmopara viticola of grapevine (preventive controlling effect)
Grapevine (Berry A) seeds were sown in the sandy loam filled in a plastic pot. After raising for 40 days in a greenhouse, the seedlings with three foliage leaves open were subjected to foliage application with a spray liquid of the suspension formulation prepared according to Formulation Example 2 which was diluted with water to a given concentration so that the liquid was sufficiently applied to the surface of the leaves. After application, the seedlings were inoculated with zoospores of Plasmopara viticola by spraying a suspension containing the zoospores. The inoculated seedlings were kept at 23°C in a damp place overnight and were further grown for 7 days in a greenhouse. The controlling effect was examined. The results are shown in Table 5.

Test Example 3

Test for controlling effect on Phytophthora infestans of tomato (curative effect)
Tomato (Ponte rosa) seeds were sown in the sandy loam filled in a plastic pot. After raising for 20 days in a greenhouse, the seedlings with two leaves open were inoculated with zoospores of Phytophthora infestans of tomato by spraying a suspension of the spores. The inoculated seedlings were kept at 23°C in a damp place overnight. The seedlings were subjected to foliage application with a spray liquid of the emulsion prepared according to Formulation Example 2 which was diluted to the given concentrations so that sufficient liquid was deposited on the leaves. After application, the seedlings were further grown for 4 days in a greenhouse, and the controlling effect was examined. The results are shown in Table 6.
Next, that the present compounds are useful as active ingredient of insecticides and/or acaricides is shown by the following test examples.

Test Example 4 (Insecticidal test on northern house mosquito)

Emulsifiable concentrates were prepared according to Formulation Example 6 and were diluted to 28500-fold with water and 0.7 ml of each solution was added to 100 ml of deionized water (concentration of the active ingredient 3.5 ppm) and therein were put twenty final instar larvae of northern house mosquito and the larvae were kept with feeding for about 8 days until all larvae in untreated section emerged and emerging inhibiting rate was examined. The results were expressed in terms of the following ratings.
(Emerging inhibiting rate)

a: 90 % or more,
b: 80 % or more and less than 90 %,
c: less than 80 %.

The results are shown in Table 7.

Test Example 5 (Insecticidal test on house fly)

The bottom of a polyethylene cup of 5.5 cm in diameter was covered with a filter of the same size as that of the bottom. An emulsifiable concentrate was prepared according to Formulation Example 6 and was diluted to 200-fold (500 ppm) with water. 0.7 ml of this diluted solution was dropped on the filter paper and 30 mg of sucrose was uniformly put therein as a feed. Therein were put 10 female imagos of house fly and the cup was closed. After 48 hours, the state of the insects was examined and mortality was obtained (two replications). The results are shown in Table 8.

Test Example 6 (Insecticidal test on larvae of brown rice plant hopper)

An emulsifiable concentrate was prepared according to Formulation Example 6 and was diluted with water to obtain a diluted liquid of 500 ppm. A stem (about 12 cm in length) of rice plant was immersed in the liquid for 1 minute. The stem was air-dried and put in a test tube. Therein were put about 30 larvae of brown rice plant hopper. After 6 days, mortality was obtained. The results were expressed by the following ratings.

a: No surviving insects were seen.
b: Five or less surviving insects were seen.
c: Six or more surviving insects were seen.

The results are shown in Table 9.

Test Example 7 (Insecticidal test on southern corn root worm)

The bottom of a polyethylene cup of 5.5 cm in diameter was covered with a filter paper of the same size as that of the bottom. An emulsifiable concentrate was prepared according to Formulation Example 6 and diluted with water (to 50 ppm in concentration). 1 ml of this diluted liquid was dropped on the filter paper and one sprout of corn was put in the cup as a feed. About 30 ova of southern corn root worm were put in the cup and the cup was closed. After 8 days, larvae hatched were examined and mortality was obtained. The results were expressed by the following ratings.

a: No surviving larvae were seen.
b: Five or less surviving larvae were seen.
c: Six or more surviving larvae were seen.

The results are shown in Table 10.

Test Example 8 (Ovicidal test on diamond back moth)

Two sprouts of radish (5 - 6 days after sown) on which ova had been deposited for 6 hours were dipped, for 30 seconds, in a liquid prepared by diluting the emulsifiable concentrate prepared according to Formulation Example 6 with water to a concentration of 50 ppm. After air-dried, the two sprouts were put in a polyethylene cup of 5.5 cm in diameter and after 6 days, mortality was obtained.
The mortality was expressed by the following three criteria.

a: 100 %,
b: 70 % or more and less than 100 %,
c: less than 70 %.

The results are shown in Table 11.

Test Example 9 (Acaricidal test on carmine spider mite)

Ten female imagos of carmine spider mites per one leaf were parasitized on a potted Phaseolus vulgaris (the first leaf) 7 days after sowing and this pot was placed in a thermostatic chamber of 25°C. After 6 days, the plant was sprayed with a liquid prepared by diluting the emulsifiable concentrate prepared according to Formulation Example 6 to a concentration of active ingredient of 500 ppm in an amount of 15 ml per one pot on a turning table and simultaneously 2 ml of the liquid was soil-injected. After 8 days, damage of the plants caused by carmine spider mite was evaluated. Criteria for evaluation of the effect were as follows.

-: Substantially no damage was recognized.
+: A slight damage was recognized.
++: The similar damage to the damage in the untreated section was recognized.

The results are shown in Table 12.

Test Example 10 (Acaricidal test on twospotted spider mites)

Each of the emulsifiable concentrates obtained according to Formulation Example 6 was diluted with water to a given concentration. 40 ml of this diluted liquid was sprayed onto two potted Paseolus vulgaris parasitized with twospotted spider mites and simultaneously the diluted liquid was soil-injected in an amount of 2 ml per one pot. The number of female imagos before the treatment, and after 11 days and 15 days from the treatment was counted and controlling value was obtained by the following formula.
The results are shown in Table 13.

Claims

A compound represented by the formula:
wherein R₁ represents a lower alkyl group, R₂ represents a lower alkyl group or a halogen atom, or R₁ and R₂ are bonded together at their termini and represent trimethylene or tetramethylene, R₃ represents a hydrogen atom, a lower alkyl group or a halogen atom, R₄ represents a hydrogen atom or a lower alkyl group, R₅ represents a hydrogen atom, a lower alkyl group or a methylthio group, and n represents 2 or 3.
A compound according to claim 1, wherein n represents 2.
A compound according to claim 1 or 2 wherein R₁ represents ethyl and R₂ represents ethyl, chlorine or bromine, or R₁ and R₂ are bonded together at their termini and represent trimethylene or tetramethylene.
A compound according to claim 1, 2 or 3, wherein each of R₃, R₄ and R₅ represents hydrogen; or each of R₃ and R₄ represents hydrogen, and R₅ represents methyl or methylthio; or R₃ represents methyl, and each of R₄ and R₅ represents hydrogen; or each of R₃ and R₄ represents methyl, and R₅ represents hydrogen or methyl.
A compound according to claim 1, 2 or 3 wherein R₃ represents methyl, and each of R₄ and R₅ represents hydrogen; or each of R₃ and R₄ represents methyl, and R₅ represents hydrogen or methyl.
A compound of the formula
A compound of the formula
A compound of the formula
A compound of the formula
A compound of the formula
A fungicidal composition which comprises as an active ingredient an fungicidally effective amount of a compound according to claim 1.
An insecticidal and/or acaricidal composition which comprises as an active ingredient an insecticidally and/or acaricidally effective amount of a compound according to claim 1.
A method for controlling insects and/or acarines which comprises applying an insecticidally and/or acaricidally effective amount of a compound according to claim 1 to the insects and/or acarines.
A method for controlling plant diseases which comprises applying an fungicidally effective amount of a compound according to claim 1 to the plants.
A use of a compound according to claim 1 as an insecticide and/or acaricide.
A use of a compound according to claim 1 as a fungicide.
A method for preparing a compound according to claim 1, which comprises reacting a compound represented by the formula,
with a compound represented by the formula,
optionally in the presence of a base, wherein R₁, R₂, R₃, R₄, R₅ and n represent the same meanings as described in claim 1, and Y represents halogen.